Five shades of green: substituent influence on the (spectro-) electrochemical properties of diferrocenyl(phenyl)methylium dyes.

Five new, intensely green diferrocenylphenylmethylium complexes 1+-5+ with electron donating (EDG: 4-MeO, 4-Me, 4-Br) or withdrawing (EWG: 3,5-CF, 4-CF) substituents were synthesized and fully characterized. The substituent influence on their electrochemical and spectroscopic properties was investigated by cyclic voltammetry, UV/Vis/NIR and -dependent EPR spectroscopy of the cationic as well as the oxidized (12+-52+) and reduced (1˙-5˙) species. The reduced forms equilibrate with their corresponding dimers (65-83%) with a clear substituent influence as expressed by their Hammett parameters in an ordering 4+ > 5+ > 3+ > 2+ > 1+.